The quaternary compound TlHgInS 3 crystallizes in a new structure type of space group C2/c with cell parameters: a = 13.916(3) Å, b = 3.9132(8) Å, c = 21.403(4) Å, β = 104.16(3)°, V = 1130.1(8) Å 3 and ρ = 7.241 g/cm 3 . The structure is a unique three-dimensional framework with parallel tunnels, which is formed by 1 ͚ [InS 33-] infinite chains bridged by linearly coordinated Hg 2+ ions. TlHgInS 3 is a semiconductor with a band gap of 1.74 eV and resistivity of ~4.32 GΩ cm.TlHgInS 3 single crystals exhibit photocurrent response when exposed to Ag X-rays. The mobility-lifetime product (µτ) of the electrons and holes estimated from the photocurrent measurements are (µτ) e ~ 3.6×10 -4 cm 2 /V and (µτ) h ~ 2.0 ×10 -4 cm 2 /V. Electronic structure calculations at the Density Functional Theory level indicate an indirect band gap and a relatively small effective mass for both electrons and holes. Based on the photoconductivity data, TlHgInS 3 is a potential material for radiation detection applications.